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Before being called up to the major leagues, Zernial played in the Pacific Coast League, the highly successful minor league circuit. In the HBO series When It Was a Game, Zernial states that he took a pay cut to come to the majors.

After he hit 29 homers for the White Sox in 1950, Zernial was sent to the Athletics in a trade that brought Minnie Miñoso to Chicago in 1951. That year Zernial led the league in home runs (33), runs batted in (129), extra base hits (68), and 17 assists in the outfield. In 1952 he hit 29 homers with 100 RBI, 42 and 108 in 1953.

Zernial was the first major leaguer to hit four home runs in the month of October during the regular season, since 1900, which he accomplished during a doubleheader on October 1, 1950. Ron Kittle would become the second player to do this in 1985.

Zernial and Al Zarilla teamed up in April 1951 to become the only players whose last names started with "Z" to play together in the same outfield. Zernial and Zarilla and played left and right field, respectively, as part of a White Sox outfield unit in four games before Zernial was traded to the Philadelphia A's at the end of April.

An aggressive fielder, Zernial twice (1949 and 1954) broke his collarbone while making diving catches. He finished his career in Detroit, primarily as a pinch hitter, hitting .323 with 10 home runs in his new role.

Zernial is featured in one of the most unusual baseball cards of all time. His 1952 Topps card shows Zernial holding a bat that has six baseballs attached to it.[2] This photo recognized that he had tied an American League record by hitting six home runs in three consecutive games from May 13–16, 1951. The day after the picture was taken, he hit his seventh home run in a fourth consecutive game.

Zernial has the second most home runs of all time among players whose last name begins with the letter Z. His 237 are second only to Todd Zeile who finished his career with 253.[3]

In a postscript to his acclaim noted above as the "new DiMaggio", Zernial figured, coincidentally, in Joe DiMaggio meeting his legendary future wife Marilyn Monroe. The "handsome" young Zernial was chosen to pose with rising star Monroe in a movie-studio publicity shot. DiMaggio was so struck by Marilyn in the photo, as well as so envious of Zernial's opportunity, that he asked the rival outfielder how to reach Marilyn.[5]